Method of producing motor fuel or gasoline from petroleum oil



June 23, 1931. M. cHAPPz-:LL 1,811,257

METHOD OF PRODUCING MOTOR FUEL OR GASOLINE FROM PETROLEUM OIL Filed Jan. 22, 1927 km wrm 5,59

Patented June 23, 1931 UNITED-"STATES PATENT oFFIcE mVIN L. CHAPPEL, OF LOS ANGELES, CALIFORNIA, ASS-IGNOR T0 STANDARD OIL COMPANY OF CALIFORNIA, 0F SAN FRANCISCO, CALIFORNIA', A. 'CORPORATION 0F DELAWARE METHOD OF PRODUCING- MOTOR FUIHI. OR GASOLINE FROM PETROLEUM'. OIL

Application nled January 22, 1927. Serial No. 162,705.

' This invention relates to a method for producing gasoline or'motor fuel from petroleum oil, and refers particularly to "a sequence of operations which will permit a 5 maximum yield of motor fuel or gasoline from crude petroleum oil with a minimum treatment with metallic halides.

Heretofore metallic halides, such as aluminum chloride, ferrie chloride, and the like,

10 have been employed in the anhydrous 'state for producing gasoline or motor fuel from hydrocarbon oils which will not yield distillates of suitable boiling points for luse as gasoline or motor fuel. vGasoline or motor troleum oil throughstraight distillation, the gasoline thus derived being usually referred to as the natural gasoline contained in the crude oil.

quired to conform to certain specifications as-to its boiling point,v for instance, those outlined in the Bureau of Mines Bulletin No. #S23-A. Such specifications require that 20 per cent. of the gasoline stock shall have boi-ling points not over 221 F.; that 50 per cent. of the gasoline stock shall have y boiling points not over 284 F.; and that 90 Ir cent. of the gasoline stock shall have iling points notover 392 F., and that the end boiling point ofthe gasoline stock shall not' be over 437. F. These specifications materially reduce tle aneunt of so-called natural gasoline that can be derived from the crude oil. Accordingly,v the usualtopping operation separates from the crude oil only a portion -of the stock having boiling pointsv within the gasoline or motor fuel.

range and there remains in the stock after treatment, a considerable percentage of oils p having boiling points ranging from approximately 290 F. to 437 F. which cannot be utilized for motor fuel due to lack of lighter ends and accordingly are customarily utilized as kerosene stocks.

Those hydrocarbons having boiling points between 131 F. and 284 F. may be, desig- 5 hydrocarbons having boiling between fuel has also been derived from crude pe-4 Gasoline ory motor fuel is generally re- 284 F. and 437 F. may be designated as fractions having boiling points within the upper gasoline range.

The obJect of the present invention is to .provide a method of producing gasoline from crude oil in which substantially all of the natural gasoline stock, including the lbeforementioned heavy ends ofthe gasoline stock, may be separated from the stock and used 1n the production of gasoline conforming to the required specifications.

Another object of the present invention is to rovide a process adapted for producing thegleficient light stock required for such gaso ine by a reaction between a metallic halide, such as aluminum chloride, and a fraction or cut of petroleum oil best adapted for the production of such stock..

Another object of the present invention is to provide a process for treating petroleum oils which will operate to produce an exceptionally high .percentage of low boiling point oils or oils within the lower boiling point range of gasoline stock. y

In accordance with the process of the present invention, crude petroleum oil is first distilled or topped to remove all of the natural gasoline or motor fuel stock that will conform to gasoline or motor fuel specifications. At the same time, a reflux' distillate from such topping, operations such, for eX- ample, as includes the kerosene cut of the petroleum 4oil and preferably also part of -the gas oil cut of the petroleum oil, is passed to a vaporizing chamber wherein the p0rtion Iof such cut having boiling point-s corresponding to the heavier gasoline or motor fuel stocks are fractionated therefrom land admixed with. the gasoline stock from the topping operation'. At this period of operation, the resultant gaoline or motor fuel stock will not properly conform to the required specifications. In order to correct such gasoline, the reflux stock from the second vaporizin operation is treated with aluminum chloride or other metallic halide under regulated conditions ofLtempera-ture, pressure, and

`duce a gasoline or motor fuel stockhaving an .excess of high boiling point oils or oils com@` ,quantities of reagents employed so as to proing within the upper portion of the gasoline boiling point range, these stocks thenbeing added or admixed with the natural gasoline stock. In this way, the process results in the production of a very large amount of gasoline or motor fuel of the required specifications from a crude oil while at the same time, there is a minimum conversion of high boiling point oils to low boiling point oils require Various further features of the present invention will be understood from a description of a preferred form or example of a process embodying the invention. For this purpose, reference is made to the accompanying drawing in which there is diagrammatically illustrated an apparatus suitable for conducting the preferred process.

The drawing represents the apparatus diagrammatically and mainly in elevation and vertical section. L

Referring to the drawing, 2 indicates an initial vaporizing chamber or topping still which is preferably mounted over a furnace 3 provided with the burner 4 or other suitable means by which said still may be heated. The still 2 is provided with a residual draw-olf line 5 and also with a crude oil inlet line 6.

The still 2 is provided with the vapor dome 7 connected with the vapor line 8 leading to a dephlegmator or reflux tower 9. Preferably in the upper portion of said dephlegmator are provided lines'10 through which the crude oil in line 64 passes, thereby providing a control over the discharge temperature of the vapors from the dephlegmator and also preheating the crude oil in the still 2. It is understood that the dephlegmator 9 may be of any usual or preferred construction of tower adapted for fractionally separating petroleum vapors. The dephlegmator 9 is provided with a vapor line 11 which leads to a condenser 12k and hence to a tank 13 for receiving the produced gasoline or motor fuel.

The reux tower 9 is provided with a line -14 by which the oils condensed therein may be withdrawn and passed to a still or vaporizing chamber 15. The still 15 is provided with suitable heating means, such as the furnace 16 having the burner 17. The still 15 has a vapor dome 18 connected with the'vapor line 19 leading to a dephlegmator or reiuX ,tower 20. Said dephlegmator 20 is also preferably provided with lines 21 through which the crude oil in line 6 passes for conserving the heat of the vapors and for lowering the discharge temperature thereof. The vapors pass from dephlegmator 20 to line 22 which preferably connected with the vapor line The lower end of the dephlegmator 20 is connected by a line 23 having a valve 24 to a pump 25, the outlet end of which is connected by the line 26 with a reaction cham tween the still 15 and the line 23. The reaction chamber 27 may be of any suitable construction adapted for contacting metallic halide and petroleum oil, preferably being designed for operation under high pressures.A The reaction chamber 27 is indicated as provided with a shaft 30 mounting a plurality of Scrapers and agitator members' 31 by which the contents of the still may be agitated and the sides maintained free of coke or sludge. The reaction chamber 27 is preferably mounted over a furnace 32 having the'burner 33 or other suitable means by which the contents of the reaction chamber 27 may be heated. 34 indicates a feeding device for introducing metallic halide into the reaction chamber and 35 indicates a vapor line leading from the reaction chamber to the dephlegmator` -l 20. Said vapor line is indicated as including a pressure dam or regulating valve 36. Thereis also provided a line 37 having a valve38 leading from the storage tank 13 to the inlet end of pump 25`by which a portion of the gasoline stock may, if desired, be

passed into reaction chamber 27 for purposes hereafter explained'.

The preferred process as carried out in the apparatus described, is as follows: Crude petroleum oil iscontinuouslypassed through line 6 into vaporizing chamber or still 2. Within said vaporizing chamber or still 2, the crude oil is heated to a temperature sulficient to vaporize therefrom all of the motor n fuel or gasoline stock. The` still temperature required normally is around 550 to 650 F. Within the still 2 all of the gasoline or motor fuel stock is vaporiz'ed together with kero- `sene and part o f the gas oil stock of the crude.

The residual crude is continuously withdrawn from line 5.

The vapors evolved in still 2 pass through line 8 into dephlegmator 9 wherein said vapors are subjected to fractionation to separate therefrom all of the stock which will produce a motor fuel of correct specifications. For example, the temperature of the vapors discharged yfrom dephlegmator 9 is usually maintained around 300 F.,.and the gafoline or motor fuelstock separated conforms to said stock has boilingpoints not over 221 F., 50 per cent. not over 284 F., 90 per cent. not over 392 F., end point'not over 437 F. v

A reflux distillate having a boiling point range of for example, between 290 and 630F. is continuously conducted from the reflux tower line 14 into still 15. Said reflux distillate condenses a considerable quantity of stock having boiling points lying in the upper motor fuel or gasoline range and the stock also includes the kerosene and some gas oil fractions. Within the'still 15, said stock is continuously subjected to vaporizathe following specifications: 20 percent. of

A tion utilizing in part its residualdheat at a temperature suflicient to at least vaporize from said oil all of 'the stock having boiling The vapors from still are passed through.

- line 19 into dephlegmator 20 whereinall the oil having boiling points within the gasoline stock is'separated and the remaining oils condensed and collected." The gasoline stock derived from 'this operation continually passes oil and intermingles with the gasoline stock from dephlegmator 9 and the twostocks are condensed in condenser 12, Were such two operations the only source of materials flowinginto the gasoline tank 13, the

resultant stock therein would not conform to gasoline or motorfuel speciications becauseV of a lack of proper low boiling point sock.

. pump and hence into reaction chamber 27 for reaction with metallic halide for the production of such high boiling.` point stock. Within reaction chamber 27, said oils continuously come into contact with metallic halide supplied from the charger 34 under regulated conditions to produce a low boiling point naphtha, adapted to provide the low boiling point constituents in which the vstock in tank 13 is deficient.

The amount of aluminum chloride used in reaction' chamber 27 may be varied, depending upon the petroleum oil treated and the products desired. lIn practice, I prefer to' use from 1li of a -pound to as high as 11/2 2 pounds of anhydrous aluminum chloride per gallon of oil charged.

In order to cause the metallic halide and hydrocarbon oil reaction in chamber 27 to produce this character of stock, the reaction is preferably conducted under hi h pressure suchas, for example, -poun s gage or i higher, and the temperature is preferably around 500 to v7 00 F. Generally the higher the temperature and pressure, the lower will be the boiling point of the stock produced.

point stock can The quantity of low boiling dition of larger also be increased byl'the a amounts of metallic halide. y

The residual metallic halide sludge is preferably continuously withdrawn from line 40r while the vapors of produced low boiling point stock are passed through line 35 and pressure regulating valve 36, and hence through dephlegmator 20 to condenser 12,v

finally entering the-gasoline or motor fuel receiver 13 wherein the three sources of supply fro-m said tank are`V blended lto form a' motor fuel-of the'required specifications.

At times, a certain quantity of soline or motor fuel may be passed` from t e receiver the lighter the hydrocarbon fed into reaction 'chamber 27 the lower the boiling'point of,

the products of the reaction will be.

' As a result of the process of the present 'invention all of the constituents of crude oil lying within the boiling point range of gasoline o`r motor fuel may be utilized for this purpose with the minimum artificial producv tion of motor fuel for correction of the boilin point range of the product.

t is to beunderstood that the still 15 and the dephlegmator 20 may be omitted from this operating process without departing from the spirit of the invention. In this case, the evolved vapors coming from the `reaction chamber 27 would be conducted directly to 'dephlegmator 9 and there commingled and blended with the vapors from the still 2 and the refluxed oil would be conducted directly through line 14 which would be connected to the suction side of pump 25. In this case, it will be necessary to use a dephlegmator of such construction as to permit the separation of all stock within the gasoline `bolling range.

While the. process herein described is well adapted for carrying out the objects of the presentinvention, various modifications and changes may be made without departing from the invention and the l.invention includes all such modifications and changes as come within the scope of the appended claims. f

I claim:

1. A process of producing blended motor fuel comprising first distilllng from crude petroleum oil the lower boilin point fractions including gasoline stocks oiling below 437 F. and higher boiling point oil, subjecting the vapors to reiiux 4separation in which operation an overhead gasoline stock vapor is formed containing oils substantially all of which have boiling points below 437 F., while forming a reflux condensate of higher boiling point oils, re-distilling from said reflux condensate a gasolinev stock having boiling points between 284 F. and 437 F., subj ectin the remaining higher boiling point oil after t e separation of such last mentioned vapors to reaction with metallic halide under suitable temperature and pressure to decomthe end point of the fuel is not over 437 F. which comprises, subjectin crude oil to distillation while subjecting t e evolved vapors to reux actionrin said reuxing action forming as vapors a gasoline stock the boiling points of which are below 437 F., and a reux condensate stock containing oils boiling between 284 F. and 437 F. along with bligher. boiling point oils, subjecting the reflux condensate to re-vaporization to vaporize therefrom oils having boiling points between 284 F. and 437 F., subjecting the remainder of the reflux condensate to reactionwith metallic halide under conditions of temperature and pressure to decompose the same and pro- 3. A process of producing blended gasoline f conforming with the specifications that not over 20% ofthe gasoline shall have boiling points over 221 F. and not over 50% of the gasoline shall have boiling points over284 F.,

and not over 90% of the gasoline shall have boiling points over 392 F. and that the end point of the gasoline shall not be over 437 F. which comprises, rst distilling crude oil while subjecting the evolved vapors to a reflux action, in said reflux action evolving as vapors oils boiling below 437 F. while forming alcondensate'which includes, along with heavier oils, oils dboiling between 28.4 and 437 F., vaporizing .from the condensed oils those fractions havin boiling points between 28.4 and 437 F., su jecting the remaining condensed oils to reaction with metallic halide under temperature and pressure conditions.

sufficient to decompose the oils to form mainly low boiling point oils containing suliicient fractions having boillng points within the range of 437 F. and 284 F., so that theselow boilin point' oils when blended with the oils have llioiling points between t284 and 437 F.` and the oils produced with vapors.

. gether.

. distilling and removing from crude petroleum -oil a vapor the boiling points of which corre- 4. A process of producing blended motor fuel which conforms to the specifications that j 20% of the fuel shall have boiling points not over 221 F., 50% shall have boiling points not over 284 F.,90 shall have boiling points not over 392 F. and that the end boiling point shall not be over 437 F. which comprises, irst spond to the above specifications, while simultaneously forming a reflux condensate, vaporizing from said reflux condensate oils hav- -ing boiling points between 284 F. and 437 F., subjecting the remainder of the reflux condensate to decomposing action with metallic halide under suitable temperature and pressure conditions to form low boiling point oils bolhng mainly below 284 F. and blending the oils produced from said first distillation with the oils boiling between 284 and 437 F. and with the oils produced from said metallic halide reaction boiling mainly below 284 F. so as to produce a motor fuel which conforms with the above set Aforth specifications.

5. A process of producing a blended motor fuel which comprlses vaporizing from crude petroleum oil the gasoline boiling point fraction together with higher boiling point fractions, subjecting the vapors to a reiiux separation wherein the gasoline boiling point fraction is left as an overhead vapor while the remaining higher boiling point fractions are condensed,revapori'zing the condensed oil to separate therefrom those fractions having relatively high boiling points within the gasoline range and a further overhead vapor, subj ecting the oil remaining 'after the separation of such last mentioned fractions to reaction with metallic halide under suitable temperature and pressure to decompose the oil and form fractions having relatively lower boiling points within the gasoline range, and

`sene fraction as a condensate, vaporizing the kerosene fraction to separate therefrom those fractions having relatively high boiling points within the gasoline range, subjecting the remaining kerosene fraction to reaction with metallic halide under conditionsof temperature and pressure to decompose the same and produce sufficient fractions having relatively low boiling points within the gasoline range to produce specification gasoline when blended with the fractions having relatively high boiling points within the gasoline range which were vaporized from said `kerosene fraction, and mixing all of the gasoline fractions so produced to form a specification gasoline. l

7. A, process of producing a blended gasoline which comprises first passing crude oil containing gasoline through 'a continuous topping operation wherein both gasoline and kerosene fractions are vaporized, subjecting the vapors to reflux separation, thereby separating from said vapors those fractions which will form a specicationgasoline, and condensing the remaining vapors including those having boiling points between 284 and 437 F. but which are unsuited for speciica- `halide Aunder temperature and pressure con-fv tion gasoline because of the presence of insufcient vapors having boiling points between 137 and 284 F., 'vaporizing from'the condensed oil those fractions havingboiling points between 284 and 437 F., subjecting the remaining oil'to reaction with metallic dition's'sulicient to decompose the oil to form lower boiling Apoint oil containing sufficient fuel comprising first topping and removing from crude petroleum oil which contains gasoline those fractions -which conform to the specifications of` a gasoline stock, vaporzing from said crude o 11 a heavier distillate, including fractions having relatively high boiling points within the gasoline range, separating such latter fractions from. saidhavier oil, subjectingthe remainder. of said heavier oil'fractions to decomposing reaction with metallic halide under suitable temperature and pressurev -to form low boiling `point` fractions containing suiiicient excess of fractions having ,relatively lower rboiling Oints'within the gasoline range so that said owerboiling point oils, when -blended with said fractions' havin relatively higher boiling points within t e gasoline range, will form -a blended product conforming to specilications for gasoline stock, and so blending said fractions that thereby substantially the entire overhead from the topping operation produces specification gasoline.

Signed at Los Angeles, Calif., this l5 day of January, 1927. y

L. CHAPPEIL. 

